Anthraquinone compounds and cellulose derivatives colored therewith



Patented May 11, 1943 UNITED STATES gram OFFICE ANTHRAQUINONE COMPOUNDSAND CELLU- LOSE WITH DERIVATIVES COLORED THERE- Joseph B. Dickey andJames G. McNally, Rochester, N. Y., assignors to Eastman Kodak Company,Rochester, N. Y., a corporation of New Jersey No Drawing. ApplicationFebruary 28, 1940, Serial No. 321,336

1 Claim.

wherein R represents a member selected from the group consisting ofhydrogen, a methyl group, an ethyl group, and a propyl group, and R1represents a member selected from the group consisting of an alkylgroup, a hydroxyalkyl group, and an alkoxyalkyl group. Morespecifically, R1 may be a methyl group, an ethyl group, a propyl group,a butyl group, a cetyl group, a hydroxyethyl group, a B-hydroxypropylgroup, a 'y-hydroxypropyl group, an w-hydroxybutyl group, a glycerylgroup, a methoxymethyl group, a methoxyethyl group, a methoxybutylgroup, an ethoxyethyl group, an acetoxyethyl group, a propionyloxyethylgroup, a butyryloxyethyl group, and similar kind of alkyl andsubstituted alkyl groups. The anthraquinone nucleus maybe fur-' thersubstituted in any alpha position not already occupied by a member ofthe group of B-aminocarboxylic acid esters represented by the aboveformula, with one or more members selected from the group including ahydroxyl group, an amino group, a methyl-, ethyl--, propyl-, butyl-, orcetylamino group, a hydroxyethyl-, fi-hydroxylpropyb, v-hydroxypropyb,or glyceryl-amino group, a flmethoxethyl-, B-ethoxyethyL, s-butoxyethyb,or 'y-methoxypropyl-amino group, an allylamino group, a cyclohexylaminogroup, a cyclopentylamino group, a tetrahydrofurfurylamino group, afurfurylamino group, a benzylamino group, a ,8-phenylethylamino group, aphenylamino. group, and other similar kind of monovalent radicals.

We have found that the anthraquinone compounds of our invention, inaddition to being valuable dyestuff intermediates, are in themselvesexcellent dyes for coloring organic derivatives of cellulose,particularly cellulose acetate. Furthermore, they show a greateraffinity for organic derivatives of cellulose and a lesser aifinity formaterials such as silk or wool, than do the corresponding free acids andtheir salts, and analogous anthraquinone compounds employed heretofore.Materials such as cellulose acetate are colored by our dyesgreenish-blue to violet shades and display an excellent stability tolight and atmospheric exposure. It is an object of our invention,therefore, to prepare the compounds described in the foregoing and tocolor organic derivatives of cellulose therewith.

The anthraquinone compounds of the invention may be prepared byrefluxing in a medium consisting of an aliphatic alcohol, pyridine ordimethylaniline, a mixture comprising an aliphatic ester of aB-aminocarboxylic acid and an anthraquinone compound having one or moreof its alpha positions substituted by a group or atom capable of beingreplaced, such as an amino group, a hydroxyl group, an alkoxy group, ora halogen atom. The necessary B-aminocarboxylic acid aliphatic esterintermediates may be prepared by a number of methods, but particularlyby the method of Jean Decombe, Annales De Chimie, 18, 79-187 (1932),wherein, the acetyl hydrazones of carboxylic acid esters are preparedand then reduced by aluminium amalgam to the corresponding,o-aminocarboxylic acid esters. The invention is illustrated further bythe following examples.

Example 1 A mixture of equal molecular proportions of leucoquinizarinand ethyl-fl-aminobutyrate in 3000 c. c of methanol is heated to boilingfor a period of 6 hours. The reaction mixture is then poured into water,oxidized with sodium perborate, and the precipitated dye filtered ofi,washed and dried. The dye thus obtained has the formula:

0 NH-OH-OHr-C o 0 can and colors cellulose acetate purple shades from anaqueous suspension of the dye. If 2 moles of ethyl-B-aminobutyrate isused, there is obtained the corresponding (ii-substituted anthraquinone.In place of leucoquinizarin, there may be substituted leuco-1,4,5-trihydroxy anthraquinone, and leuco-1,4,5,8tetrahydroxyanthraquinone, and in place of ethyl-B-aminobutyrate there may besubstituted methyl-B-aminobutyrate, butyl-fi aminobutyrate,methyl-fi-aminovalerate, propy1- ,B-aminocaproate, and methyl, ethyl,propyl, butyl, and cetyl esters of ,B-aminopropionic acid. All of theabove dyes produce purplish shades on cellulose acetate.

Example 2 A mixture of equal molecular proportions of leucoquinizarin,ethanolamine, and methyl-13- amino butyrate in 1500 c. c. of butanol isheated under reflux until no further color change takes place. The dyeis then precipitated, oxidized, and recovered as described in Example 1.The dye compound thus obtained has the formula:

and colors cellulose acetate blue shades from an aqueous suspension ofthe dye. In place of ethanolamine, there may be substituted methylamine,ethylamine, propylamine, cetylamine, propanolamine, butanolamine,allylamine, tetrahydrofurfurylamine. methyl ester of e-aminopropionicacid, c-methoxyethyl ester of p-aminopropicnic acid, ,3-acetoxyethylester of p-aminopropionic acid, 1-amino-2-methoxyethane, 1- amino 2ethoxyethane, cyclohexylamine, 2- aminothiazole, aniline, benzylamine,para-phenylene diamine, and similar kind of organic amines. Themethyl-,B-aminobutyrate may be re- 3 tetraaminoanthraquinone colorcellulose acetate greenish-blue shades.

Example 3 A mixture of equal molecular proportions of leuco 1,4,5triamino anthraquinone, ethyl-flaminopropionate and propanolamine isheated under reflux in butanol until no further color change takesplace, and dye recovered as described in Example 1. Cellulose acetate iscolored greenish-blue shades from an aqueous suspension of the dye. Thecompound has the formula E!) NH-CaHsOH Instead of leuco-1,4,5-triaminoanthraquinone, there may be employed 1euco-1,4-diamino anthraquinonewhich colors cellulose acetate blue shades, leuco-l,4, 5,8-tetraaminoanthraquinone which colors cellulose acetate greenish-blue shades,leuco- -diamino 5 methylamino-B- phenylamino anthraquinone which colorscellulose acetate greenish-blue shades, and leuco-1,4-dihydroxy-5-phenylamino-8-ethylamino anthraquinone which colorscellulose acetate greenishblue shades.

the blue.

Example 4 A mixture of equal molecular proportions ofleuco-1-hydroxy-4-aminoanthraquinone, cyclohexylamine, andethyl-p-aminobutyrate in propanol is heated under reflux for a period ofabout 6 hours. The reaction mixture is then poured into water, oxidizedwith sodium perborate, and the precipitated dye filtered oil, washed anddried. The dye compound thus obtained has the formula:

chi-c111 CHz-CH:

and colors cellulose acetate blue shades from its aqueous suspensions.

Example 5 1 mole of leucoquinizarin is heated under reflux with 1 moleof aniline and 1 mole of ethyl-B- aminobutyrate in 3000 0. es. ofpyridine until no further color change takes place. The reaction mixtureis oxidized with air, and the dye crystallized by evaporation of thepyridine. The compound thus obtained has the formula O H l and colorscellulose acetate blue shades from its aqueous suspensions. In place ofleuco-1,4-diaminoanthraquinone, there may be substitutedleuco-l,4,5-triamino anthraquinone, and leuco- 1,4,5,8-tetraaminoanthraquinone both of which color cellulose acetate greenish-blueshades.

Example 6 A mixture of 1 mole each of l-methylaminoi-bromoanthraquinoneand ethylp-aminobutyrate is dissolved in 500 0.0. of dimethylaniline andheated under reflux for 24 hours or until no further color change takesplace toward The reaction may be catalyzed with copper powder, copperacetate, and other copper salts. The dye obtained by crystallizationfrom concentrated and cooled solution colors cellulose acetate blueshades from an aqueous suspension of the dye which has the followingformula:

IO NHCH:

In place of 1-methylamino-4-bromoanthraquinone there may be substituted1-ethylamino-, 1- propylamino-, 1-ethanolamino-, l-cyclohexylamino-,1-anilino-, or 1-benzylamino-4-bromoanthraquinone. All of theanthraquinone dyes prepared as described in this example color celluloseacetate blue shades.

Example 7 (I) NHQ and colors cellulose acetate purplish-blue shades froman aqueous solution of the dye.

Example 8 1 mole of leuco-l,4-diamino anthraquinone is heated underreflux with 2-3 moles of the hydroxyethyl ester of normal fl-aminobutyric acid in 3000 0.0. of pyridine until no further color changetakes place.

the dye recovered as crystals. The dye product has the formula:

and colors cellulose acetate blue shades from an aqueous solution of thedye. In place of leuco- 1,4-diamino anthraquinone, there may besubstituted leuco-1,4,5-triaminoanthraquinone, and leuco-1,4,5,8-tetraaminoanthraquinone both of which color cellulose acetategreenish-blue shades.

The solution is then oxidized with air, concentrated by evaporation, and

In the application of the anthraquinone compounds of our invention tothe coloration of cellulose acetate, the dye will ordinarily be appliedfrom an aqueous suspension which may be prepared by grinding the dye toa paste with a dispersing agent such as a soap, a sulfonatecl oil, or afatty acid glycerol sulfate, and dispersing the paste in water. Thematerial to be colored is then immersed in the dispersion starting witha temperature of about 45-55 C., which is gradually raised to 80-85 C.,at which point the material is worked for several hours. Salt may beadded to facilitate exhaustion of the dye bath during the dyeingoperation.

While our invention is illustrated more particularly in connection withcellulose acetate, it will be understood that the anthraquinonecompounds above described are by no means limited to cellulose acetatealone, but are likewise applicable to other organic derivatives ofcellulose such as hydrolyzed and unhydrolyzed organic acid esters ofcellulose or mixed organic acid esters of cellulose including celluloseformate, cellulose propionate, cellulose butyrate, celluloseacetate-propionate, cellulose acetate-butyrate, and cellulose ethersincluding methyl cellulose, ethyl cellulose, and benzyl cellulose.Further, the dye compounds of the invention are also applicable tomaterials comprising a mixture of one or more of the above mentionedorganic derivatives of cellulose, as well as to materials comprising anorganic derivative of cellulose admixed or interwoven with other textilematerials.

We claim:

The anthraquinone compound having the formula:

O NH-CH--CHz-OOOCH3 JOSEPH B. DICKEY. JAMES G. MCNALLY.

